US3281446A - Tolylene diisocyanates stabilized with 1-phenyl-2-thiourea - Google Patents
Tolylene diisocyanates stabilized with 1-phenyl-2-thiourea Download PDFInfo
- Publication number
- US3281446A US3281446A US279335A US27933563A US3281446A US 3281446 A US3281446 A US 3281446A US 279335 A US279335 A US 279335A US 27933563 A US27933563 A US 27933563A US 3281446 A US3281446 A US 3281446A
- Authority
- US
- United States
- Prior art keywords
- thiourea
- phenyl
- stabilized
- isocyanate
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 title claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 description 19
- 150000002513 isocyanates Chemical class 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 8
- -1 2,4-diethyl-phenyl -2-thiourea Chemical compound 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 150000003585 thioureas Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- LXBYWZIMFMQONU-UHFFFAOYSA-N (4-ethenylphenyl)thiourea Chemical compound NC(=S)NC1=CC=C(C=C)C=C1 LXBYWZIMFMQONU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GMEGXJPUFRVCPX-UHFFFAOYSA-N Butyl-thioharnstoff Natural products CCCCNC(N)=S GMEGXJPUFRVCPX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OTSOVXJZBYIGSK-UHFFFAOYSA-N but-1-enylthiourea Chemical compound CCC=CNC(N)=S OTSOVXJZBYIGSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 3,281,446 TOLYLENE DIISOCYANATES STABILIZED WITH 1-PHENYL-2-THIOUREA David T. Manning, South Charleston, W. Va., assignor to gnion Carbide Corporation, a corporation of New ork N0 Drawing. Filed May 9, 1963, Ser. No. 279,335 2 Claims. (Cl. 260453) This invention relates to isocyanate compositions, particularly an isocyanate composition stabilized from discoloration.
Isocyanates are typically colorless liquids or solids which are found to discolor on storage. Discoloration of isocyanates deleteriously affects their saleability typically because the color may be transferred to the product in which the isocyanate is employed. This is particularly so in the case of polyisocyanates used in resin manufacture.
It is herein provided an agent which significantly retards discoloration of the isocyanate product thus allowing storage of the isocyanate for reasonable periods of time prior to use. These agents are particularly effective when employed in solution with the isocyanate.
The agents employed in this invention for retarding discoloration of organic isocyanates are organic thioureas possessing one nitrogen atom bearing two hydrogen atoms, the other nitrogen :atom bearing at least one directlybonded aromatic ring. Of particular significance are thioureas having the formula:
wherein R and R may be hydrogen; alkyl of from 1 to 18 carbon atoms, preferably of from 1 to 12 carbon atoms; cycloalkyl, preferably of from 5 to 8 carbon atoms; aryl, preferably monocyclic, bicyclic aryl and fused aryl; alkenyl of from 2 to 18 carbon atoms, preferably of from 2 to 8 carbon atoms; cycloalkenyl, preferably of from 5 to 8 carbon atoms; alkoxy of from 1 to 18 carbon atoms, preferably of from 1 to 12 carbon atoms; aryloxy, preferably monocyclic and bicyclic aryloxy; halogen, such as chlorine, bromine and fluorine; R can be hydrogen, alkyl of from 1 to 12 carbon atoms, alkenyl of from 2 to carbon atoms, cycloalkyl of from 5 to 8 carbon atoms or and preferably hydrogen; n is an integer of from 0 to 5; m is an integer of from 0 to 5; and the sum of n and m is equal to 5.
Exemplifications of the aforementioned class of thioureas include l-phenyl-Z-thiourea,
1- Z-methylphenyl) -2-thiourea,
1t- (2,4-diethyl-phenyl -2-thiourea,
1- 3-butylphenyl -2-thiourea, l-(4-octadecylphenyl -2-thiourea, l-( 1-n aphthyl -2-thiourea,
1- (Z-naphthyl -2-thiourea, l-(phenanthryl -2-thiourea,
1-( 1 -benzanthryl -2-thioure a, 1-(4-vinylphenyl) -2-thiourea,
1- [3 (Z-butenyl phenyl] -2-thiourea, 1- [4- S-hexenyl phenyl] -2-thioure a, 1- (4-vinyl-3-methylnaphthyl) -2-thiourea,
3,281,446 Patented Oct. 25, 1966 Ice 1- (4-cyclohexylphenyl) -2-thioure a,
1- [4- 3 -cyclohexenyl phenyl -2-thiourea, 1- Z-methoxyphenyl -2-thiourea,
1- Z-phenoxyphenyl -2-thio-urea,
1- (4-butoxynaphthyl -2-thiourea, 1t-(2-chl0rophenyl)-2-thiourea,
1-( 4-bromonaphthyl -2-thiourea,
1- S-fiuorophenanthryl -2-thiourea, l-phenyl- 1 -methyl-2-thiourea,
l-phenyl- 1 -butyl-2-thiourea,
l- Z-methylphenyl) l Z-ethylhexyl -2-thiourea, 1- l-n-aphthyl l 3-butenyl -2-thiourea, 1- (4-vinylphenyl) -1-cycloheXyl-2-thiourea, l-phenyl- 1 -cycloheptyl-2-thiourea, bis(1-phenyl)-2-thiourea,
bis[ 1- (Z-methylphenyl) ]-2-thiourea,
bis( lr-phenanthryl -2-thiourea, bis[1-(3-butenyl-2-phenyl) ]-2-thiourea,
and the like. 2-thiourea.
The isocyanates which may be treated to retard discoloration are organic monoand polyisocy-anates, such as aliphatic, cycloaliphatic and aromatic mono-, di-, triand/or other poly isocyanates which tend to discolor under conditions of moisture and temperature typically associated with industrial storage procedures. Illustrative of organic isocyanates which are beneficially stabilized from discoloration include the following:
The most preferred thiourea is l-phenyl- The particular color retardation agent selected (color stabilizing agents) should be capable of dissolution in the particular isocyanate to be stabilized regardless of whether the isocyanate is a liquid at ambient temperature or must be warmed to transform it to the liquid state. The selected agent should be stable at the temperature of the isocyanate at the time of incorporation, and incorporation be effected at a temperature below that of decomposition or of any undesirable reaction of the isocyanate with itself or the agent. The agent, or mixtures of the agents, should be employed in the isocyanate in any amount sufficient to retard discoloration. Usually that amount falls between 0.005 and 5 percent by weight of the isocyanate. Preferably, the agent is employed in amounts from about 0.01 to 1.0 percent by weight of isocyanate. In general, this invention is directed to employing an amount of the agent sufficient to retard discoloration of the isocyanate.
The following serves to specifically illustrate operation of this invention, however, it is not intended to limit the scope of this invention:
A dry 8-ounce glass bottle is purged with dry nitrogen and charged with a mixture of 150 grams of colorless, pure, freshly-distilled tolylene diisocyanate (80 weight percent 2,4-tolylene diisocyanate and 20 weight percent 2,6-tolylene diisocyanate) and 0.15 gram of 1-phenyl-2- thiourea. The resulting composition is blanketed under dry nitrogen and the bottle securely sealed by wrapping its stopper with tape. A similar sample is repared, but without the added 1-phenyl-2-thiourea, for use as a blank.
Both the blank and the l-phenyl-Z-thiourea test samples are stored in the dark at room temperature, about 25 C. Examination of the blank and thiourea samples after storage for 22 days reveals the development of a significantly deeper yellow color in the blank. After 5 /2 months, the l-phenyl-Z-thiourea sample is unchanged 4 and exhibits a significantly weaker yellow color than did the blank after only 22 days of storage.
Though the above relates to specifics of the present invention, this invention is not intended to be restricted thereby except insofar as these specifics appear in the claims.
What is claimed is:
1. A solution of tolylene diisocyanate and from about 0.005 to 5 percent by weight of said diisocyanate of 1 phenyl-Z-thiourea.
2. A solution of tolylene diisocyanate and from about 0.01 to 1.0 percent by weight of said diisocyanate of 1- phenyl-2-thiourea.
References Cited by the Examiner UNITED STATES PATENTS 2,885,421 5/1959 Spiegler 260453 CHARLES B. PARKER, Primary Examiner.
IRVING MARCUS, JOSEPH P. BRUST, Examiners.
DALE R. MAHANAND, Assistant Examiner.
Claims (1)
1. A SOLUTION OF TOLYLENE DIISOCYANATE AND FROM ABOUT 0.005 TO 5 PERCENT BY WEIGHT OF SAID DIISOCYANATE OF 1PHENYL-2-THIOUREA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US279335A US3281446A (en) | 1963-05-09 | 1963-05-09 | Tolylene diisocyanates stabilized with 1-phenyl-2-thiourea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US279335A US3281446A (en) | 1963-05-09 | 1963-05-09 | Tolylene diisocyanates stabilized with 1-phenyl-2-thiourea |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3281446A true US3281446A (en) | 1966-10-25 |
Family
ID=23068526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US279335A Expired - Lifetime US3281446A (en) | 1963-05-09 | 1963-05-09 | Tolylene diisocyanates stabilized with 1-phenyl-2-thiourea |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3281446A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639502A (en) * | 1984-05-08 | 1987-01-27 | Bayer Aktiengesellschaft | Substantially colorless organic polyisocyanates, processes for their production and their use in the production of polyurethane plastics |
| US20070213496A1 (en) * | 2006-03-10 | 2007-09-13 | Thomas Savino | Uretonimine-modified isocyanate composition and method of forming the same |
| US20070213432A1 (en) * | 2006-03-10 | 2007-09-13 | Thomas Savino | Uretonimine-modified isocyanate composition and method of forming the same |
| US20230399942A1 (en) * | 2022-06-08 | 2023-12-14 | Saudi Arabian Oil Company | Fluorescent dye oil tracer compositions |
| US11999855B2 (en) | 2021-12-13 | 2024-06-04 | Saudi Arabian Oil Company | Fluorescent dye molecules having hydrophilicity and hydrophobicity for tracer applications |
| US12286574B2 (en) | 2021-12-13 | 2025-04-29 | Saudi Arabian Oil Company | Manipulating hydrophilicity of conventional dye molecules for tracer applications |
| US12440821B2 (en) | 2021-12-13 | 2025-10-14 | Saudi Arabian Oil Company | Method for tracing subterranean formations with oil-soluble organic molecular tracers and extracting them of from oil phases |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2885421A (en) * | 1956-01-27 | 1959-05-05 | Du Pont | Stabilization of organic isocyanates |
-
1963
- 1963-05-09 US US279335A patent/US3281446A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2885421A (en) * | 1956-01-27 | 1959-05-05 | Du Pont | Stabilization of organic isocyanates |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639502A (en) * | 1984-05-08 | 1987-01-27 | Bayer Aktiengesellschaft | Substantially colorless organic polyisocyanates, processes for their production and their use in the production of polyurethane plastics |
| US20070213496A1 (en) * | 2006-03-10 | 2007-09-13 | Thomas Savino | Uretonimine-modified isocyanate composition and method of forming the same |
| US20070213432A1 (en) * | 2006-03-10 | 2007-09-13 | Thomas Savino | Uretonimine-modified isocyanate composition and method of forming the same |
| US7504523B2 (en) | 2006-03-10 | 2009-03-17 | Basf Corporation | Uretonimine-modified isocyanate composition and method of forming the same |
| US7541397B2 (en) | 2006-03-10 | 2009-06-02 | Basf Corporation | Uretonimine-modified isocyanate composition and method of forming the same |
| US20090143542A1 (en) * | 2006-03-10 | 2009-06-04 | Thomas Savino | Uretonimine-Modified Isocyanate Composition and Method of Forming the Same |
| US7777054B2 (en) | 2006-03-10 | 2010-08-17 | Basf Corporation | Uretonimine-modified isocyanate composition and method of forming the same |
| US11999855B2 (en) | 2021-12-13 | 2024-06-04 | Saudi Arabian Oil Company | Fluorescent dye molecules having hydrophilicity and hydrophobicity for tracer applications |
| US12286574B2 (en) | 2021-12-13 | 2025-04-29 | Saudi Arabian Oil Company | Manipulating hydrophilicity of conventional dye molecules for tracer applications |
| US12440821B2 (en) | 2021-12-13 | 2025-10-14 | Saudi Arabian Oil Company | Method for tracing subterranean formations with oil-soluble organic molecular tracers and extracting them of from oil phases |
| US20230399942A1 (en) * | 2022-06-08 | 2023-12-14 | Saudi Arabian Oil Company | Fluorescent dye oil tracer compositions |
| US12188350B2 (en) * | 2022-06-08 | 2025-01-07 | Saudi Arabian Oil Company | Fluorescent dye oil tracer compositions |
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